TW323281B - - Google Patents

Description

A7 B7 323281 V. Description of the invention (I) The present invention relates to the N-transacid methylimidodiacetic acid (" PMIDA ") of formula U): H0 〇

\ I P-CH ^ -NiCHj-C00H) 2 ⑴

HO and N-saccharinic acid methylglycine, the compound I Ye formed the heavy green intermediate plaque of NR acid methylglycine (" glyphosate "), which is a transferred, later, broad Effective weeding falcon. In the past, glycerol was prepared by gasifying PMIDA in different ways. For example, U.S. Patent No. 3,954,848 shows that it is catalyzed by acid? 》 104 gasification-hydrolysis reaction to produce glycine salt. To be specific, PMID A is pseudo-mixed with water and acid and then heated with heating. Then, a gasifying agent such as pergasified hydrogen is added to convert PM.IDA to the glyoxylate, and then separated by precipitation. U.S. Patent No. 3,969,398 shows the gasification of PMIDA into glyceroate, using molecular gas-containing gas, such as air, oxygen, gas diluted with krypton, argon, nitrogen or other inert gas, gas-hydrocarbon mixture, etc. The activity is broken into a catalyst. U.S. Patent No. 4, 147,719 shows a specific single 91 or a single aqueous solution reaction system in which PMID A salt is vaporized with a molecular gas-containing gas in the presence of platinum supported by an active substrate to produce a specific monoglycolate 91 or Second, the oxidation reaction is carried out at an atmospheric pressure of 1.5 to 5 kg / cm2 or higher. U.S. Patent No. 4,898,972 shows that a cobalt salt or a manganese salt is used to oxidize PMID A in the presence of bromide ions to produce a glycine salt. One 3-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public daughter) (please read the precautions on the back before filling out this page) —----- LINE 'Ministry of Economic Affairs Central Bureau of Industry and Fisheries Consumption Cooperative printed «.

L A7 B7 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention description (>) US Patent No. 4,002,672 shows the hydrolysis of PMID A with acid catalysis to produce glyoxylate and its salts, ^ 11) 4 You have a strong acid with a value lower than 2.2 and contact with it at elevated temperature to cause the decomposition or hydrolysis of linoleic acid methyl bis-acetic acid into N-sacrylic acid methyl-glycan acid or other decomposition products. U.S. Patent No. 3,954,898 shows a variety of gasification agents, including over-gasification.-»·, Which can be present in acetic acid or stronger acids, at 70_100 ° CT, to gasify PMIDA into glyphosate. U.S. Patent Nos. 4, 6 9 6-, 7 7 No. 2 shows that the activity of catalytic cracking can be enhanced by first removing the gasification compounds from the surface. As can be seen from the above, the tamarinic acid methylglycine can be prepared by gasification of tamarinic acid methyliminodiacetic acid by several techniques. However, with the exception of a few, the above technology will produce emissions containing formaldehyde and toxic metals and / or strong acids. The use of extremely strong acids at elevated temperatures requires the use of corrosion-resistant equipment. Even worse. Some of these technical boxes are conducted under dilute dilution conditions, so it takes a lot of energy to concentrate the solution to allow the salicylate product to be recovered economically. Oleic acid methylglycine can also be co-catalyzed by precious metals. It is prepared by gasification of beta or formic acid by-products, and it is prepared by oxidation of PMIDA with oxygen-containing gas. In the presence of precious metals, the gasification of PMIDA in the absence of active sulfur does not produce any products , See US Patent No. 3,950,402. The disadvantage of using noble metal catalysts is that they are very expensive and are coated with polymers, as shown in US Patent No. 4,579, 689, or they are placed in crystalline inorganic matrix capsules such as the US Patent No. 4,582,650 shows that it is protected from rapid amine deactivation. According to US Patent No. 4,147,719 ,? 》 16 salt can be made directly? 》 (10-person salt (please read the precautions on the back before filling out this page) Order ί. 绻

__L This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 323281 V. Description of the invention (+) It is produced by using a gas-containing gas in the presence of a precious metal supported by an active sulfonate matrix and a gasification catalyst such as platinum . Again, although the conversion is high, the catalyst is expensive. Therefore, it is necessary to be very careful during the manufacture of the product so as not to lose any catalyst. The use of the precious metal catalyst can be used to formaldehyde co-products, which are simultaneously gasified to greatly reduce the need to remove this co-product from the final reaction product. Cost and time. This W 19 patent teaches that the use of an active master catalyst alone cannot simultaneously vaporize formaldehyde, and in fact it also increases the production of undesirable by-products. Therefore, the purpose of the present invention is to provide a process for preparing methyl glycine acid Can eliminate the shortcomings of the previous technology process. The object of the present invention is to provide a process for preparing phosphonic acid methylglycine, which can eliminate wicking emissions and minimize catalyst cost. Printed by the Ministry of Economic Affairs, Central Bureau of Economic Affairs, Beigong Consumer Cooperative (Please read the precautions on the back before filling out this page) The problem of the prior art has been overcome by the present invention, which provides a nearly constant child yield for the preparation of oxalic acid A The process of glycine acid. At the same time, toxic by-product formaldehyde can be gasified into formic acid and CO 2 or its salts. In general, the process of the present invention eliminates the need to use precious metals and the accompanying problems. The gas-containing gas system is replaced with more chemically active over-vaporized hydrogen. After combining with active sulfonic acid, PMIDA can be gasified into PMG in high yield, and formaldehyde by-products can be oxidized into formate and C02, leaving non-toxic The effluent can be easily degraded by biodegradation. The rate of addition of β vapors needs to be carefully controlled and monitored. Figure 1 is a diagram of typical gasification of PMIDA with pergasified hydrogen and activated sulfon; and the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) A7 _B7_____ 5. Description of the invention (4)圔 2 is a diagram of vaporizing PM ID A according to Example 5. The starting material, PMIDA, can be prepared by conventional methods known to those skilled in the art, for example, by combining formaldehyde, iminodiacetic acid and n-acid in the presence of a strong acid such as hydrogen helium acid or Sulfuric acid down reaction · The resulting N_R acid methylimino diacetic acid mixture can be used directly in the following process, or N_ succinic acid methyl-imino diacetic acid can be used in the following process before the process as the starting material before the reaction Separate it from the mixture. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page)-Line 1 According to the present invention, the oxidation_ can be inorganic pergasification, preferably hydrogen peroxide Will be breathless, jealous of the air, succumbed to each other. In the present invention-embodiments, the gas-containing gas can be used to vaporize most PMIDAfi and then to complete the reaction with personates. More specifically, because the gas-containing gas suitable for the present invention is generally cheaper than over-gasification, about 60-90% of PMIDA gasification, preferably 70-80% PMID A gasification can be performed by gas-containing gas, so , Peroxide can be used to complete the gasification of PMIDA and formaldehyde generated by gasification. After about 90% of the PMIDA has been gasified by the gas containing gas, it is not suitable to add the radon compound, because tamping in the unreacted PM ID A seems to prevent the PMG from being vaporized by the gasified compound. The right time to use hydrogen peroxide is determined by the balance between the cost savings of using gaseous gas and the tolerable amount of PMG bad gasification due to overgasification. Preferably, the portion of oxidant used needs to be determined To maintain the gas concentration in the exhaust gas at least below about 10%, preferably below about 3%.

The active sulfone catalysts used in the present invention are commercially available, and include Morit SX + and RO 0.8, Darco KB, Calgon RB, RD, CAL.CPG and BL -6-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7_ printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs. 5. Description of the invention (r). For example, granular or powdery active bases are suitable. The active master should have a specific surface area from 1D0 to 2000 square meters / gram, preferably about 400 to about 1600 square meters / gram. The active sulfur can be used in a range from about 0.1 unit / PMIDA to more than about 10 units / PMIDA, just like a cladding type continuous ore reactor. For batch reactions, the preferred ratio of He to PMID A ranges from about 0.2 to about 0.4. Surprisingly, the inventors of the present invention found that if the feed rate of H202 is continually adjusted when the if reaction is mixed, the content of the exhaust gas is kept at a low level, such as less than about 10%, preferably less than about 3%, Then the decomposition of H2〇2 into 〇2 and H20 by active sieve will only become an unimportant side reaction, but those skilled in the art know that the gas fi in the exhaust gas is controlled at a higher concentration (such as 50% or 20%). To increase the cost of raw materials * By controlling the concentration of O2 in the exhaust gas of the mine to control the gasification, the reaction rate is allowed to reach the highest. Surprisingly, the inventor of this case also showed that not only the gas of the co-product CH20 The gasification rate is faster than that of all known conditions of PMIDA gasification, and when all PMIDA has been exhausted, the 02 concentration increases rapidly at a rate greater than 5%. This phenomenon has been confirmed by HP LC analysis, and when PM ID A is converted to the maximum value of PM G and the undesirable gasification of PM G is the smallest, this reaction can be allowed to stop β. For example, when the gas concentration exceeds When the speed increases by about 20%, this anti-plaque can be stopped. Preferably, the oxidation is carried out at a temperature of about 3 (TC to about just below the boiling range of K), more preferably at about 5 (TC to about 65 eC. At higher temperatures, formic acid by-products tend to be with The acid salt product reacts to produce water-soluble N-formyl-glycolate (HCO-PMG), which in turn can be vaporized into N-formyl-amine. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297mm) (please read the note item on the back and then fill in this page)-Order · 11 Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative A7 B7 V. Description of invention U) Methyl domain acid. When at a lower temperature During the next operation, the formation rate of HCO-PMG decreases faster than the gasification rate. The reaction temperature and active concentration should be selected to provide a short reaction time and minimize the formation of HCO-PMG. Methylimino diacetic acid The concentration in water should be from about 1% to about 60% or higher. Preferably, the concentration is from about 35% to about 55%. For the PMG salt, a suitable N-linoleic acid methylimidinyl diacetate can be used as a starting material Prepared by. The proper formation of salt cations include age gold hurricane, earth metal test, trimethyl anion, granidiniu, urea, ammonium and organic (When the organic group is an aryl group, this ammonium salt is a primary amine salt) includes those prepared from organic amines such as alkylamines, alkyleneamines, and alkyl alcoholamines containing no more than 2 amine groups, such as methylamine, ethyl Amine, η-propylamine, isopropylamine, η-butylamine, isobutylamine, sec-butylamine, η-pentylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine , Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, decylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl Amine, methyltetradecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, di Ethylamine, di-η-propylamine, diisopropylamine, di-η-pentylamine, diisoamylamine, dihexylamine, di-heptylamine, didecylamine, trimethylamine, triethylamine, tri-η-propylamine , Tri-isopropylamine, tri-η-pentylamine, ethanolamine, η-propanolamine, isopropanolamine, diethanolamine, H, N-diethylethanolamine, H-ethylpropanolamine, butylethanolamine, Allylamine, n_butenyl-2-amine, η-pentenyl-2-amine, 2,3-dimethyl Butenyl-2-amine, di-butenyl-2-amine, η-hexenyl-2-amine and propylene diamine; initial arylamines such as aniline, methyl aniline, ethyl aniline, ο, β , ρ- This paper scale is applicable to China National Standard (CNS) Α4 specification (210X 297mm) ---------- ^ I- ----- Subscribe ----------- Line {JI (Please read the precautions on the back before filling in this page) Printed 328281 by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (7) Methylamine * Phenyldiamine «2, 4, 6 -Tribromobenzamine «benzidine» lysine $ 〇, ancestor. P- aniline aniline and the like; and heterocyclic amines such as pyridine morpholine. Hydropyridinium 9 pyrrolidine, indole 1 dopamine t Aza And the like 〇 The present invention will be easier to understand after referring to the special but non-limiting examples 9 Ο It should be understood that the present invention is not limited by these steps, it is only for display purposes Carried out under the spirit and scope of the present invention Example 1 PHIDA acid (0.375 Μ) slurry, 〇.56M 28% ammonium reaction, producing a slurry equivalent to 25% PM I DA acid 9 Molar mixed solution of monoammonium salt and diammonium salt Ο 40 grams of active sodium (C a 1 go η type RB mill Powder) After adding this slurry,% m quickly mix this slurry. 0 10.2% Η 2 〇. 'Ί solution is added into the slurry at a rate of 0.57 5 g / min. 9 until a total of about 2.3M is added. During the addition, the reaction flask was immersed in an unheated or cooled water bath, so that the temperature during the reaction was maintained between 25 ° C and 30 ° C. Periodically, the sample was taken out 9 filtered to remove solids and analyzed by HP LC 〇Amazingly f When gas is used instead of Η: »0 2 time * No m or any other common impurities are found 9 Wait until you add nearly t ± s» 成 成 9 There are only few PN ID Α Waiting for the stage of gasification. Only PH G, a small amount of formic acid and the amount of H-formaldehyde-PMG are found. Example 2 Repeat Example 1, except for the PMI DA- Propylamine salt as the starting reactant and 9 using 25% Η 2 billion 5 ί > necessary to achieve the same results. Example 3 Repeated implementation of Example 1, except that PNI DA's tri-sodium salt was used as the starting reactant 9 and 50% Η 2 〇 2 1 〇 tri-sodium salt was not gasified like a lower salt. 1.1 —-I-— — — Aunt J----n B— I L--II Line f on 1 (please read the precautions on the back before filling this page) This paper scale is applicable to China National Standard (CNS) A4 Specifications (210X297mm) A7 B7 V. Description of the invention (no) Endeavour Example 4 Fill a 500ml Parr pressure bottle with water and PMIDA (0.375M) and if necessary. Quantitative falcon, and active master (granular or powder), the contents are stirred with a magnetic mixer, and heated with a heating belt to maintain the desired reaction temperature. When necessary, pressurize the pressure bottle and use the back pressure control valve to maintain the desired pressure; otherwise, vent the pressure bottle to the atmosphere. Persistently monitor the% 〇2 value in the exhaust gas from the reactor and record the reaction conditions every minute. Table 1 lists the operating conditions of the 42 groups of experiments. Typically the internal value of the exhaust gas is less than 10% at the lower reaction temperature, and when the reaction temperature is raised, the exhaust gas must not contain free 02. When about 2 equivalents of H202 were added, the% 02 value increased rapidly, showing that the PMG forming reaction was completed. This conclusion has been determined by HPLC analysis of the sample. Table 2 lists the results of 42 groups of experiments. Figure 1 shows a typical gasification graph. H- 1 n mu n. ^ ^^^ 1 ^ — ^ 1 IJ i K ^ i & ^ nn n Anf 、-口 系 一 -4 (Please read the precautions on the back before filling in this page) Central Ministry of Economic Affairs Bureau of Standards, Beigong Consumer Cooperative Printing Policy-10-This paper scale is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) B7 5. Invention Description (9) Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs [ -M W2〇2 / min. / M ΡΜΙΟΛ | Γ o.oi ίο I | 0.009Q | | 0.0215 1 § oo 〇ooooosoo 'I 0.0175 1 〇ooo' | 0.0139 1 I 0.0163 | \ 0.0171 | I 0.0163 1 1 0.0131 I «0 oo 0.0093 1 0.000 7 1 0.0092 1 0.0092 1 0.0005 1 0.0093 | 0.0093 | 0.0044 1 0.0040 1 0,0001 1 0.0107 1 0.0U8 1 0.0055 1 0.0109 1 0.0091 1 0.0094 1 0.0094 1 o.oi 11 1 0.09 / 0 1 0.1150 1 0.0103 1 0.0091 1 0.0U5 I 0.0107 1 o.ons 1 1% Η202 1 10.2 | 25.0 I 50.0 1 50.0 1 50.0 1 50.0 I 50.0 1 50.0 1 50.0 I 50.0 I 50.0 | | 50.0 | 1 50.0 | 1 50.0 I r ^ SQ.O 1 1 50.0 1 I 50.0 | | 50.0 | 1 50.0 I 1 50.0 | I 50.0 | 1 50,0__I I 50.0 |! 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 1 50 . 0 1 50.0 | 50.0 1 50.0 I 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 5M_ 50.0 1 1 Μ Η202 / Μ ΡΜΙΟΛ S e > o 1 2.62 o 1 2.02 o 1 2.00 os 1 2.31 oo 1 2,09 IM (M (M CM CM rw CM CM CM (si CM CM 2.04 | oi 2.04 1 2.04 1 1 2.04 I 204 1 ♦ S5 * mmr〇o 1 37.5 tn r »tn r« · tn f «o | 37.5 37.5 | p 埘 mc 0 1 0 1 cto 〇〇〇 < β c to sa tn tn ssssm rk to rs. O to ss «/ 9 r * · tn so * 〇o < ao 2 S s 〇sooosssscm 1 W3 saa 1 WH.1 1 na \ | MOI rt 1 i-Pf-nniino 0 1 c. IPr-amlno i-Pr-omina | i-Pr amine | e • Ξ = c. 〇1 (8 c. HPr amine | i-Pr amino | I Pr * amino | j-Pf amirm 1 I Pr amlim o S C. a QO i j-Pf omino I 9 i! C.-I Pr-amino I 9 II c c. 2 Vs a " T cco O Γ3 〇CNJ 1 /) oooo 丨 丨: 〇〇1 oooooo 〇〇cccgo 〇〇ccoc on 3 O * 5 C! Tt • 1 U g 1 i U s 1 c 〇 " S «i (3 2 K 1 Cl I 0 5 3 ji 3 r § ϋ > 3 ± C e 8i 3 > 'I ae 3 £ i _C! O ffi co X 1 > sic 〇1 Calqon 19R Pulv. | Caloun Pulv. | (3 S <. · = Q aa W < 1 m «O * δ 〇r4oii (SX Plus | Calgon RB Pulv. 1 Calnon Rft Pulv. 3 S i Λ 〇 日 cs * 3 Calnon Pulv. | CalQon Ming f'ulv. ≫ J ic § 3 Calnon AB Pulv. | Calnon AB Pulv. 1 AI _c 1 s 1 o Γ / alnon CPGl2x-uj c X «Μ δ 2_ 1 > 1 $ 1 i • 1 13 ξ rg 5 O o " s | Ϊ Έ 1 (3 τ CM 5 " 5 1 of C 7 f 3 1 3 gl C3 f 2.13 I 2.13 I 2.13 I 2.13 I 2.13 I 2.t3 | 2.13 1 2,13 1 2.13 I 1 2.13 I 2.13 I 2.t3 1 2.04 < 〇cx V 1 0.52 I β.52 1 17.40 I 1 J7 .40 I | 17.40 II 0.52 I 1 ml 2.13 I 2.13 I 2.t3 I 6.52 I 3.40 I 2.t3 | 2.13 I 2.13 I n csj 2.13 1 on 〇2.13 \ 2.13 I 2.t3 2.13 l 2.13 Γ3 II n I % PMIDA 25.0 I 25.0 I 25.0 1 25.0 I 25.0 I 2S.0 I 25.0 I 25.0 I 2S.0 I 2S.0 1 25.0 IO to 04 " ~ '»: 5 ....... 25.0 o tn« V 25.5 25.0 25.0 1 25.0 I 1 25.0 I 1 «6 I! 25.0 25.0 I 25.0 I 2S.0 I 25.0 25.0 25.0 I 25.0 25.0 -2S: 0 ~ 25.0 25.0 2S.Q 25 * 0— om Of —25 * 0 25 0 oi «n Γ cr 250 '2i〇1 K > Rui u-CM «(O to o cs o-n ▼ W) < 〇f *» CD as CM CM CM ▼ tn CNJ iD 1 f- «Μ e CM σ» C > 4 〇r > n Γ) oo tn n iO n O 1 I 〇 > o O ▼ ▼ < N »(please read the precautions on the back before filling this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) _B7 5. 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ol 〇rj -r -12 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The A7 B7 is printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (") Example 5 The 500ml Parr pressure bottle is equipped with a sintered stainless pin (ss) spray tube for distributing 02, a similar tube for sampling, a magnetic stirrer, a l / 8 " ss 100Ω DIN Pt RTD, — The top has an ss air condenser with a pressure relief valve set at 60 psi, a pressure gauge, a vent valve and an adjustable back pressure control valve. Fill the bottle with 200 grams of 112 0, 160 grams of PM ID A and 40 grams of Nor it SX + active master. The container was heated and maintained at 60 ° C with an electric hood and the temperature was controlled by the Macintosh II running Workbench ™. Use a Microelectrodes, Inc. gas probe and meter to monitor the O2 concentration in the exhaust gas at the back pressure control valve ^ The O2 probe is held by fixing it in a small set of receivers Constant temperature. The amount of 02 entering the reactor is measured by a 0-2 liter / min Sierra mass flow controller. The output value layer from the 02 counter and the mass flow controller is input to Mac + Workbench ™ ^ The flow setting value input to the mass flow controller is from Mac + Workbench ™. The temperature, 02 flow rate,% 02, and d% 02 / dt are plotted on the computer and the data are recorded every minute. This result is shown graphically in 圔 2. When the gold part P M ID A is oxidized, 6:40 starts with oxygen, and the 02 concentration increases rapidly. By measuring the value of d% 02 / dt, that is, the rate of change of% 02, this (sudden increase) point becomes obvious during the reaction. If necessary, the gas flow can be automatically closed. In this case, when the rate of change increases to > 20% 02 / hour, an alarm will be activated, and the O2 will be turned on and off manually. After cooling to room temperature and allowing to stir overnight, the liquid sample is analyzed by HPLC-13- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) ---------- M J ----- Subscribe——l · ---- Line & Η I (Please read the notes on the back before filling this page) 323281 A7 B7

V. Description of the invention (· >) The following results were obtained: N-methylaminomethyl sulfonic acid (MeAMPA) Aminomethyl phosphonic acid (AMPA) N-methyl-PMG 0.1% ~ 0.1% 0.4% Economic Ministry of Central Standards Bureau Beigong Consumer Cooperatives printed formaldehyde 6% PMG 2.7% formic acid 3.2% N-formyl-PMG, ~ 0. 15¾ PM IDA micro cellar Example fi Repeat Example 5, but halve PMID A 80 grams to shorten the reaction time by 50%. After 160 minutes of oxygen flow, or when the amount of 02 required to complete 80% of the reaction is completed, stop sampling the liquid for HP LC analysis. The formaldehyde concentration was 2.1% (but if 160 grams of ΡΜΜΑ were injected as in Example 5, it would be ^ 4.2%) < »Visible ungasified PMIDA, but not quantitative. The pressure was vented to the atmosphere and 50% H202 was slowly pumped into the back-mix mixture while adjusting the H202 pumping rate to maintain the% 02 in the exhaust gas at 10%. When 15.5 grams (H202) was added, no unreacted PMID A was found in the liquid and the formaldehyde concentration dropped to 1.2%. Very slowly add more 50% H202 while maintaining the temperature at 60 ° C. After a total of 27.3 grams (H202) was added, the liquid was sampled and analyzed by HPLC. The formaldehyde concentration dropped to 0.17% and AMPA increased from no increase to 0.6% and MeAMPA was 0.4%. -14 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page)

Claims (1)

A8 B8 C8 D8 Nangqi 86. 8. 2S No. 8 5 1 Θ ^ Τ31ΙΓ ^ ™ BΊΕΓ®Methylimino diacetic acid for the simple synthesis of methyl glycine of oxalic acid. Patent case (86 years Amended in August), the scope of patent application ^ 1. A method for preparing N-phosphonomethylglycine or its salt, which includes: (a) in a container, a gasification agent that is necessary to overgasify hydrogen, In the presence of an active master, to gasify N-oxomethyl-glycine or a salt thereof at a temperature effective to produce the N-oxomethyl-glycine or a salt thereof; (b) from this The container discharges the gaseous reaction product; (c) monitors the oxygen concentration in the gaseous reaction product; and (d) adjusts the tolerance to the N-phosphonic acid at any given time according to the gas concentration monitored by the gaseous reaction product The amount of the oxidizing agent reacted with methylimino diacetic acid. 2. The method as claimed in item 1 of the patent application scope, in which the amount of the oxidant is adjusted so that the gas concentration of the gaseous reaction product does not exceed about 50%. (Please read the precautions on the back and then fill out this page) The amount of the order is overdose, and the gas will be concentrated in the oxygen, and the anti-term state of the production method should be the first one. 'Special section, please apply for the increase of %%. The printing volume of the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is about the amount of overdose, and the degree of concentration should be in the gas. The product should be $ JU1 * ·' " Inverse terms should be favored by others, please adjust it in the special section. Apply for%. If you add 10 parts of the overdose to make the gas more concentrated, the oxygen will be used in it. The anti-state of the production method 1. The gas should be used in the surrounding area. Please pay attention to the special section. Add% 3 by Du Wen in countering the legal terms in the countermeasure ix Fang Fanli, please apply for Ru Rubian! The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) A8 '丨 Xiuyu 1 Mu Nian P B8 C8 D8 VI. Shen Zhuwei 86. 8. 2 3 Central Ministry of Economic Affairs Industrial and consumer cooperatives are restricted from 2 Q ° to about 15 G. 7 · For example, the cracking method of item 1 of the patent scope, where the reaction is carried out at a temperature from about 50 ° to about 65 ° C. 8. If the method of applying the patent item 1 of the patent scope, the active master has a The surface area is about 100 to about 2000 square meters / gram. 9. The method as claimed in item 1 of the patent application, wherein the active master has a specific surface area of about 400 to about 1600 square meters / gram. 1 〇. As claimed in the first paragraph of the patent application, the preparation method, wherein the initial ratio of active master to oxalic acid methyl iminodiacetic acid is between about 0.01 to about 1 (U 11. As in the application of the patent application of the first preparation method, Wherein the initial ratio of the active master to oxalic acid methylimidodiacetic acid is between about 0.1 and about 1. 12. As in the method of claim 1 of the patent application scope, the active master to the oxalic acid methylimino diacetic acid The initial ratio is from about 0.2 to about 0.4. 13. The method of claim 1 of the patent application scope, in which the N-oxalic acid is allowed when the oxygen concentration in the gaseous reaction product increases at a rate exceeding 20% per hour The amount of oxidizing agent in the reaction of iminodiacetic acid will be reduced to zero. 14. A method for preparing N- knee acid methylglycine acid or its preparation, which includes: including: (a) N-oxalic acid methyl-imine The diacetic acid or its salt is fed to the container; (b) The gas containing gas, in the presence of active sulfonate, and at a temperature that can effectively produce the N-phosphonomethylglycine or its salt, to oxidize the N -Methyl-imino diacetic acid; (c) The gaseous reaction product is discharged from the container; (d) The gaseous reaction product is monitored Concentration; and -1 6-This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) ~ Order 111 final (please read the notes on the back before filling this page) A8 32328 ^ 6. 8. 2 ^ 11 D8 6. Apply for reference 8. (e) When the gas monitoring concentration increases at a rate exceeding 20% per hour, stop feeding the N-oxalic acid methyl-iminodiacetic acid or its salt. 15.- A method for preparing H- knee acid methylglycine acid or its salt, which includes: (a) feeding N-oxalic acid methyl-iminodiacetic acid or its salt to a container; (b) containing gas Gas, in the presence of active sulfonate, and at a temperature that can effectively produce the N-tartaric acid methylglycolic acid or its salt, to oxidize 70-80% of the N-tartaric acid methyl-iminodiacetic acid; (c ) The gaseous reaction product is discharged from the container; (d) The oxygen concentration in the gaseous reaction product is monitored; (e) After the pervaporation of hydrogen is used to gasify all residual N-phosphonomethyl-iminodiacetic acid or Its salt; and (f) when the oxygen monitoring concentration increases at a rate exceeding 2 ϋ% every hour, stop feeding the N-oxalic acid methyl-iminodiacetic acid or its salt. ---..- ------------- Order hl l · ---- 0 (Please read the precautions on the back before filling in this page) Printed by the Beigong Consumer Cooperative of the Central Rubbing Bureau of the Ministry of Economic Affairs -17- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297mm)